RUI: CAS: Solvent-Free Synthesis of Transition Metal Halide Clusters

RUI：CAS：过渡金属卤化物簇的无溶剂合成

• 批准号: 2247482
• 负责人: Dean Johnston
• 金额: $ 27.12万
• 依托单位: Otterbein College
• 依托单位国家: 美国
• 项目类别: Standard Grant
• 财政年份: 2023
• 资助国家: 美国
• 起止时间: 2023-06-01 至 2026-05-31
• 项目状态: 未结题
• 来源: https://www.nsf.gov/awardsearch/showAward?AWD_ID=2247482&HistoricalAwards=false
• 关键词: RUI; CAS; Solvent; Free; Synthesis

With the support of the Chemical Synthesis program in the Division of Chemistry, Professor Dean Johnston of Otterbein University will develop new synthetic routes to substituted transition metal halide cluster materials that have potential future applications in bioimaging, liquid crystal and optical devices, catalysis, oxygen sensing, and as X-ray contrast agents. This family of clusters is strongly phosphorescent and has unique electrochemical properties, making the clusters potentially useful for a wide range of applications. The central cluster core is very stable, making it an ideal building block for the creation of new chemical constructs that link cluster units to form chains or three-dimensional networks. It is important to note that current solution-based methods for preparing modified clusters are severely limited by the reactivity and solubility of the products, restricting the types of materials that can be generated and isolated. This project seeks to overcome obstacles associated with current synthetic techniques. The research team will use thermal heating and mechanical grinding of metal cluster salts to prepare novel materials with potential applications for optical devices and sensing. Undergraduate students at Otterbein University will engage with this project through summer research experiences and activities integrated into the Inorganic Chemistry laboratory, gaining valuable experience in independent research and the synthesis and characterization of inorganic materials. These research experiences will complement the activities of the Cardinal Science Scholars Program, an NSF-supported program of academic, co-curricular, and non-academic activities demonstrated to increase retention and graduation in science, technology, engineering, and mathematics (STEM).This research project is directed toward the preparation of metal cluster synthons that are intended to serve as building blocks for new molecules and materials and to allow for precise control over connectivity and dimensionality of cluster materials. Greater than ninety-five percent of all known metal halide cluster derivatives are homoleptic, illustrating the difficulty in selective ligand substitution using solution-based synthetic routes. The Johnston research team will prepare metal halide cluster salts where the cation is selected to react with the anionic cluster, using charge balance and the properties of the cation to control the stoichiometry of the reaction. Reactions will be initiated by thermal or mechanochemical means in the absence of solvent, thereby avoiding complications from solvent interference or solubility issues. The reactions and products will be analyzed using thermogravimetric analysis, in-situ Raman spectroscopy, and powder and single-crystal X-ray diffraction methods. The results of this research are expected to provide researchers in the field of inorganic cluster chemistry with synthetic tools and pathways to prepare new cluster-based materials.This award reflects NSF's statutory mission and has been deemed worthy of support through evaluation using the Foundation's intellectual merit and broader impacts review criteria.

在化学系化学合成项目的支持下，奥特拜因大学Dean Johnston教授将开发替代过渡金属卤化物簇材料的新合成路线，这些材料在生物成像、液晶和光学器件、催化、氧传感等方面具有潜在的未来应用，并作为X射线造影剂。该簇簇具有强烈的磷光性，并具有独特的电化学性质，使得该簇簇具有广泛的应用前景。中央簇核非常稳定，使其成为创建新化学结构的理想构建块，这些新化学结构将簇单元连接起来形成链或三维网络。值得注意的是，目前基于溶液的制备修饰簇的方法受到产物的反应性和溶解度的严重限制，限制了可以生成和分离的材料类型。该项目旨在克服与当前合成技术相关的障碍。研究小组将利用金属簇盐的热加热和机械研磨来制备具有光学器件和传感潜在应用的新型材料。奥特拜因大学的本科生将通过暑期研究经验和融入无机化学实验室的活动来参与该项目，获得独立研究以及无机材料的合成和表征方面的宝贵经验。这些研究经验将补充卡迪纳尔科学学者计划的活动，该计划是一个由 NSF 支持的学术、课外和非学术活动计划，旨在提高科学、技术、工程和数学 (STEM) 的保留率和毕业率。该研究项目旨在制备金属簇合成子，旨在作为新分子和材料的构建块，并允许精确控制簇材料的连接性和维度。所有已知金属卤化物簇衍生物中超过 95% 是均配的，这说明使用基于溶液的合成路线进行选择性配体取代的困难。约翰斯顿研究小组将制备金属卤化物簇盐，其中选择阳离子与阴离子簇反应，利用电荷平衡和阳离子的性质来控制反应的化学计量。反应将在没有溶剂的情况下通过热或机械化学方式引发，从而避免溶剂干扰或溶解度问题引起的复杂化。将使用热重分析、原位拉曼光谱以及粉末和单晶 X 射线衍射方法来分析反应和产物。这项研究成果有望为无机团簇化学领域的研究人员提供制备新型团簇材料的合成工具和途径。该奖项反映了 NSF 的法定使命，并通过利用基金会的智力价值进行评估，认为值得支持以及更广泛的影响审查标准。